Anthraquinone dyes

ABSTRACT

NOVEL DYES WHICH ARE 1,4-DIHYDROXY-8-AMINO-ANTHRAQUINONES HAVING IN THE 5-POSITION AN UNSUBSTITUTED OR SUBSTITUTED AMINO GROUP AND IN THE 7-POSITION AS ALKOXY, PHENOXY, MERCAPTO OR THIOPHENYL GROUP, ARE PRODUCED BY REACTING A 1,4-DIHYDROXY-8-AMINO-ANTHRAQUINONE WHICH CONTAINS IN THE 5-POSITION AN UNSUBSTITUTED OR SUBSTITUTED AMINO GROUP AND IN THE 7-POSITION A HALOGEN, PHENOXY OR SULFONIC ACID GROUP WITH A MERCAPTAN, THIOPHENOL, ALCOHOL OR PHENOL. AFFINITY OF THE DYES CAN THE IMPROVED BY HALOGENATION.

United States Patent 3,801,606 ANTHRAQUINONE DYES Hans-Samuel Bien,Burscheid, Walter Hohmann and Heinrich Vollmann, Leverkusen, andHeinrich Leister, Cologne-Stammheim, Germany, assignors to BayerAktiengesellschaft, Leverkusen, Germany No Drawing. Continuation ofabandoned application Ser. No. 571,431, Aug. 10, 1966. This applicationMay 25, 1970, Ser. No. 41,689

Int. Cl. C09b 1/50 U.S. Cl. 260-380 4 Claims ABSTRACT OF THE DISCLOSURENovel dyes which are l,4-dihydroxy-8-arnino-anthraquinones having in the5-position an unsubstituted or substituted amino group and in the7-position an alkoxy, phenoxy, mercapto or thiophenyl group, areproduced by reacting a 1,4-dihydroxy-8-amino-anthraquinone whichcontains in the 5-position an unsubstituted or substituted amino groupand in the 7-position a halogen, phenoxy or sulfonic acid group with amercaptan, thiophenol, alcohol or phenol. Affinity of the dyes can beimproved by halogenation.

This case is a continuation of Ser. No. 571,431, filed Aug. 10, 1966,now abandoned.

This invention comprises new and valuable anthraquinone dyes, and theproduction and use of the same.

The new dyes are l,4-dihydroxy-8-amino-anthraquinones which contain inthe 5-position an unsubstituted or substituted amino group and, in the7-position, an alkoxy, phenoxy, mercapto or thiophenyl group which mayoptionally contain halogen.

They are obtainable according to the invention when1,4-dihydroxy-S-amino-anthraquinones which contain an unsubstituted orsubstituted amino group in the 5-position and halogen or a phenoxy orsulphonic acid group in the 7-position are reacted with mercaptans,thiophenols, alcohols or phenols and the obtained dyes optionallyafterhalogenated.

The new dyes are particularly suitable for the dyeing and printing ofsynthetic fibres.

The amino group in the 5-position of the anthraquinones used as startingmaterial may be primary, secondary or tertiary. As substituents, itcontains preferably hydrocarbon radicals such as alkyl radicals(preferably up to 6 carbon atoms), aralkyl radicals, cycloalkylradicals, preferably the cyclohexyl radical or aryl radi cals preferablyphenyl radicals, which may optionally contain further substituents suchas halogen (e.g. chlorine or bromine), hydroxy, alkyl (preferably loweralkyl radicals), alkoxy (preferably lower alkoxy radicals), cyano,amino, nitro or carboxylic ester groups, preferably of lower aliphaticcarboxylic acids. The term lower alkyl designates in this applicationcompounds containing up to 4 carbon atoms.

Examples of the substituted 1,4-dihydroxy-anthraquinones used for theprocess according to the invention are:

7-bromo-8-amino-5-methylamino-, 7-bromo-8-amino-5-ethylamino-,7-bromo-8-amino-5-butylamino-, 7-bromo-8-amino-5-}3-oxyethylamino-,7-bromo-8-amino-5-' -oxypropylamino-,7-chloro-8-amino-5-p-ethoxy-ethylamino-, 7 -bromo-8-amino-5--y-butoxypropylamino-, 7-bromo-8-amino-5-fl carbethoxyethylamino-,7-bromo-8-amino-5-isopropylamino-, 7-bromo-8-amino-5-tert.-butylamino-,6-bromo-5,8-diamino-,

3,801,606 Patented Apr. 2, 1974 7-bromo-8-amino-5-cyclohexylamino-,7-br0mo-8-amino-S-p-methylcyclohexyl-amino-,7-bromo-8-amino-5-benzylamino-, 7-bromo-8-amino-5-u-phenylethyl-amino-,7-bromo-8-amino-5-fi-phenyl-ethylamino-, 7-sulpho-8-amino-5-anilino-,7-phenoxy-8-amino-5-auilino-, 7-bromo-8-amino-5-o-toluidino-,7-bromo-8-amino-5-m-toluidino-, 7-bromo-8-amino-5-p-toluidino-,7-bromo-1-amino-5-o-anisidino-, 7-phenoxy-8-amino-5-o-anisidino-,7-chloro-8-amino-5-m-anisidino, 7-bromo-8-amino-5-p-anisidino-,7-sulpho-8-amino-5-m-chloroanilino-,7-chloro-8-amino-5-p-chloroanilino-, 7 -bromo-8-amino-5-p-phenetidino-,7-bromo-S-amino-5-m-acetylamino-anilino-,7-bromo-8-amino-5-p-oxymethylanilino-, 7-bromo-8-amino-5-m-oxyanilino-,7-bromo-8-amino-5- (p-methoxy-m-chloro-anilino)-, 7-bromo-8-amino-S-[p-(hydroxyacetamino)-anilino] 7 -bromo-'8-arnino-5-p-fluoro-anilino-1,4-dihydroxyanthraquinone. I

The mercaptans and alcohols or thiophenols or phenols used for thereaction may be the simple compounds, but may also be substitutedcompounds which contain e.g. hydroxyl groups, alkoxy groups, halogens,lower alkyl radicals or possibly alkyl-mercapto groups.

The mercaptans contain preferably hydrocarbon radicals with up to 6carbon atoms and contain as substituents preferably hydroxyl, loweralkoxy or carboxylic acid ester groups. The alcohols also containpreferably hydrocarbon radicals with up to -6 carbon atoms which maythemselves contain as substituents preferably hydroxyl, lower alkoxy orphenyl groups. The phenols or thiophenols are preferably compounds ofthe benzene series which contain as substitutents preferably halogen(e.g. chlorine or bromine), lower alkyl radicals (e.g. methyl, ethyl ortertiary butyl radicals), which may themselves again be substituted, egby hydroxyl groups (e.g. hydroxyethyl groups) or lower alkylmercaptogroups. Examples of such compounds are the following: methylmercaptan,ethylmercaptan, butylrnercaptan, hexylmercapt-an, cyclohexylmercaptan,benzylrnercaptan, mercaptoethanol, thioglycerin, 3-mercaptobutanol-l,thiophenol, o-methylthiophenol, o-chlorothiophenol, m-bromo-thiophenol,p-carbomethoxythiophenol, m-carbethylthiophenol, methanol, ethanol,butanol, glycolmonomethyl ether, glycolmonobutyl ether, glycol,cyclohexanol, phenol, m-cresol, p-chlorophenol, o-bromophenol,resorcinolmonomethyl ether or methylmercaptophenol. The process ispreferably carried out in a solvent, e.g. in methanol, ethanol, butanol,isopropanol, dimethylformamide, N-methyl-pyrroldine, chlorobenzene orglycolmonomethyl ether. The reaction may be carried out both at roomtemperature and at elevated temperature, e.g. at temperatures in therange between 20 and 200 C. It is also possible to work in the presenceof acidbinding agents, e.g. in the presence of alkali metal carbonates,acetates, hydroxides, alcoholates or also tertiary amines.

The new dyes are finely divided in the customary manner, eg by pastingfrom sulphuric acid or an organic solvent and subsequent grinding orkneading with dispersing agents. They dye (according to the printing anddyeing processes known in practice) synthetic material of eg polyester,polyamides or triacetate in blue to green shades in very good fastnessesto wet processing, sublimation and thermofixation as well as goodlight-fastness. By mixture of individual dyes, as also by halogena tion,the afiinity can be improved. The halogenation may therefore be carriedout in customary manner with halogens such as chlorine or bromine, orwith conventional agents which split off halogen, such asbromosuccinimide, sulphuryl chloride or N-bromo-p-toluene-m-sulphamide.Solvents used are for example sulphuric acid (20-90%), hydrochloricacid, nitrobenzene, chlorobenzene, o-dichlorobenzene, glacial aceticacid. The halogen may enter both in an external aryl nucleus and intothe anthraquinone nucleus. Preferably, therefore, on average 0.1 to 1halogen radical per anthraquinone molecule is introduced.

In the examples, the parts stated are parts by weight and thetemperatures are degrees Celsius.

EXAMPLE 1 (a) A mixture of 8.6 parts7-bromo-8-amino-5-cyclohexylamino-1,4-dihydroxy-anthraquinone. 4.3 partssodium carbonate, 90 parts glycolmonomethyl ether and 3.1 partsthioglycol is heated to 120 C. for 45 minutes and 45 parts water areadded dropwise in the cold. The crystalline product is filtered off withsuction, washed with water, and the residue is boiled up in 150 partsacidified water. After being filtered off with suction it is washedneutral and dried. 6.7 parts (-=78% of the theory) amino 8cyclohexylamino-7-B-hydroxyethylmercapto- 1,4-dihydroxy-anthraquinoneare obtained.

(b) 10 parts skein material of polyethyleneglycolterephthalate are dyedat 9698 C. for two hours after addition of sulphuric acid until apH-value of 4.5 is set up in a liquor consisting of 600 parts water, 0.1part of the dye of Example 1(a) in finely divided form, 3.4 parts of amixture of o-, m-, p-cresotic acid methyl ester and 06 part of a mixtureof equal parts aralkylsulphomate and a non-ionic polyglycol ether.Rinsing and drying are then effected. The fastness to rubbing can beimproved if after-treatment is carried out for 10-30 minutes in a gentlyboiling bath which contains, per 1000 parts water, 5.5 parts causticsoda solution of 38 B., 2 parts sodium dithionite and 1 part of apolyglycol ether of a fatty acid amide. A clear, bluish-green dyeing ofgood to very good fastnesses, in particular of excellent fastness tosublimation, is obtained.

(c) 10 parts flock of polyethyleneglycolterephthalate are dyed for 2hours at 120-130 C. in a liquor (pH 4.5) consisting of 400 parts waterand 0.15 part, in the most finely divided form, of the dyepreparedaccording to Example 1(a), as well as 0.3 part of a mixture of equalparts aralkylsulphonate and a non-ionic polyglycol ether. After rinsingand drying, a clear, bluish-green dyeing is obtained.

(d) A fabric of polyester fibre material, prepared from terephthalicacid and 1,4-bis-hydroxymethylcyclohexane is impregnated on the paddingmangle with a liquor which contains, in 1000 parts water, parts of thedye of Example 1 in finely divided form as well as 10 parts of athermosol auxiliary, in particular a polyethylene ether, such as isdescribed e.g. in Belgian patent specification No. 615,102.

The fabric is then squeezed to a weight increase of 70% and dried in asuspension nozzle drier or in a drying cabinet at 80 to 120 C.Thereafter the fabric is treated with hot air for about 45 seconds at180 to 220 C. in a stenter or in a jet hot flue, after which it isrinsed, possibly subjected to a reductive after-treatment, and dried.The reductive after-treatment for the purpose of removing particles ofdye adhering superficially to the fibres may take place in such a mannerthat the fabric is entered at 20 to C. into a liquor containing 3-5ml./l. caustic soda solution of 38 B. and 1-2 g./l. hydrosulphite,heated to 70 C. within 15 minutes and left for a further 10 minutes.This is followed by acidification with 2-3 ml./l. 85% formic acid at 50C., rinsing and drying. A clear, bluish-green dyeing is obtained.

(e) If the fabric of polyester fibre material is replaced by one ofpolyamide, prepared from hexamethylenediamine and adipic acid, andotherwise the same procedure as described in Example 1(d) is followed,but without reductive after-treatment, a clear, bluish-green dyeing ofgood to very good fastnesses is obtained.

(f) The fabric of polyester fibre material is replaced by a fabric oftriacetate and otherwise the same procedure as described in Example 1(d)is followed. A clear, bluish-green dyeing of good fastness is obtained.

(g) 10 parts skein material of a polyamide (prepared by condensation ofcaprolactam) are slowly heated to the boil and dyed at the boil for 1hour in a liquor which contains, in 400 parts water, 0.2 part, in finelydivided form, of dye prepared according to Example 1(a), and 0.2 g. of acustomary dispersing agent. A clear, bluishgreen dyeing is obtained.

(h) 10 parts skein material of cellulose triacetate are dyed at 96-98 C.for one hour after adjustment to pH 5 (with formic acid) of the pH-valuein a liquor which contains 400 parts water, 0.2 parts in finely dividedform of dye according to Example 1(a), 3.4 parts of a mixture of o-, m-,p-cresotic acid methyl ester and 06 part of a mixture of equal partsaralkylsulphonate and a nonionic polyglycol ether. A clear, bluish-greendyeing is obtained.

(i) 100 parts cellulose triacetate as combed material are dyed for 2hours at 120 to 130 C. in a liquor of pH 4.5 consisting of 1000 partswater and 1.5 parts, in the most finely divided form, of the dye ofExample 1(a) as well as 3 parts of a mixture of equal partsaralkylsulphonate and a non-ionic polyglycol ether. After rinsing anddrying, a clear, bluish-green dyeing is obtained.

EXAMPLE 2 (a) 8.8 parts 7-bromo-8-amino-5-p-toluidino-quinizarin, 4.3parts sodium carbonate, 90 parts glycolmonoethyl ether and 3.1 partsthioglycol are heated to 120 C. for one hour, filtered off cold withsuction and Washed with glycolmonoethyl ether until there is a slightlygreen run-off. The filter residue is boiled up in 100 parts acidifiedwater, filtered off hot with suction and washed neutral. 7 parts (=80%of the theory) 8-amino-5-p-toluidino-7-B-hydroxyethylmercapto 1,4dihydroxy-anthraquinone are obtained.

(b) The dye may be dyed according to the various methods which aredescribed in Examples 1(b) to (i). Thus, for example according to 1(c)there is obtained on polyester material a green dyeing of good to verygood fastnesses, above all of excellent fastness to sublimation; andaccording to 1(g), on polyamide green dyeings also are obtained.

(c) The dyes stated in the following can be prepared and dyed accordingto the method of Example 2 when the equimolar amounts of the appropriatestarting compounds are used.

Yiel

1, Ex. percent Shade Dye 78 Somewhat bluish green. 76 Green.

EXAMPLE 8 (a) 13.9 parts7-bromo-5,8-diamino-l,4-dihydroxy-anthraquinone, 6.4 parts sodiumcarbonate, 70 parts glycolmonomethyl ether and 6.6 parts thiophenol areheated to C. for 1 hour; 60 parts methanol are then added 5 dropwise at60 C. followed by 7 parts hydrochloric acid at 20-30" C. Thecrystallized residue is filtered ofi with suction and washed withmethanol. After being boiled up in 100 parts acidified water it isfiltered off with suction, washed neutral and dried. 14.5 parts (=96% ofthe theory) 5,8-diamino-7-phenylmercapto-1,4-dihydroxyanthraquinone areobtained. According to Example l(b), the dye yields on polyestermaterial a strong, clear, greenish-blue dyeing of good fastness tosublimation and light.

(b) According to analogous methods the following dyes may be prepared,which for example according to l(d) give blue dyeings with goodfastnesses.

Yield, percent Shade 92 Greenish blue.

9. 5,8-diamino-7-o-methylphenylmercapto-l,4-dihydroxy-anthraqui- DyeEXAMPLE 14 (a) A mixture of 8.8 parts7'bromo-8-amino-S-p-toluidino-1,4-dihydroxy-anthraquinone, 4.3 partssodium carbonate, 90 parts glycolmonomethyl ether and 4.4 partsthiophenol are heated to 120 C. for 1 hour, filtered 01f cold withsuction and washed with glycolmonomethyl ether and methanol. The residueis boiled up in 100 parts acidified water, filtered off with suction andwashed neutral. After drying, 8.8 parts (=94% f the theory) 8 amino-p-toluidino-7-phenylmercapto-1,4-dihydroxyanthraquinone are obtained.

(b) According to Example l(d), a green dyeing very fast to sublimationand a good light-fastness is obtained.

(c) Analogously to Example 14, the following compounds may also beprepared and dyed:

Yield, percent Shade 88 Reddishblue.

15. 8-amino-5-p-toluenesulphamido-7- phenylmercapto-l,d dihydroxy Dyeanthraqumone.

16-..- 8'amino-5-o-anisidino-7-phenyl- 92 Green.

mercapto-l,4-dihydroxy-anthraqumone.

17---. 8-amino-5-cyclohexylamino-7-phenyl- 89 Blue-green.

mercapto l,4-dihydroxy-anthraquinone.

EXAMPLE 118 EXAMPLE 19 7.0 parts7-bromo-5,8-diamino-1,4-dihydroxy-anthraquinone, 25 parts phenol and 1.1parts potassium hydroxide are heated to 180 C. for 9 hours. Aftercooling of the mixture to 80 C., 25 parts methanol are added dropwise;this is followed by filtration with suction and washing phenol-free withmethanol. The residue is then boiled up with 1'00 parts acidified water,filtered off with suction and 6 washed neutral. 5.2 parts (=72% of thetheory) 5,8-diamino-7-phenoxy-1,4-dihydroxyanthraquinone are obtained inthe form of blue needles. When dyeing is elfected according to Examplel(g), a clear, blue dyeing of good fastness to light and sublimation isobtained.

EXAMPLE 20 7.6 parts 7-bromo-8-amino-5-methoxypropylamino-1,4-dihydroxy-anthraquinone, 4 parts thiophenol, 3.8 parts sodium carbonateand 75 parts glycolmonoethyl ether are heated to 120 C. for 1 hour andthe crystalline substance which is obtained is filtered oif cold withsuction. The filter residue is washed with glycolmonoethyl ether untilthere is a greenish-blue run-01f and then it is washed with methanol.The reaction product is then boiled up in 100 parts acidified water,filetred 01f hot with suction, washed neutral and dried. 6.4 parts (=79%of the theory) dye are obtained which, dyed according to Example l(b),gives clear, blue-green shades of very good fastness to sublimation.

EXAMPLE 21 8.4 parts 8-amino-S-anilino-7-3-hydroxyethylmercapto-1,4-dihydroxy-anthraquinone are heated to 60 C. in 85 parts nitrobenzeneand at this temperature 0.64 part bromine are added dropwise. After 2hours the nitrobenzene is removed by steam distillation and the residuewhich is formed is filtered off with suction and washed neutral. Thebromination product contains 3.1% bromine. 0n polyester material thereis obtained, for example according to Example l(b), a green dyeing ofoutstanding fastness to sublimation.

EXAMPLE 22 8.4 parts 8-amino-5-anilino-7-/3-oxyethylmercapto-1,4-dihydroxy-anthraquinone are suspended in 85 parts 20% hydrochloric acidand, after addition of 0.64 part bromine, stirred for 20 hours at roomtemperature. After filtration with suction, washing neutral with hotwater and drying are effected. 8.4 parts of the bromination product(bromine content: 2.3%) are obtained. On polyamide fibre material thereis obtained according to Example l(f) a green dyeing with good fastnessto wet processing.

EXAMPLE 23 1.7 parts boric acid are dissolved at C. in 35 parts 50%sulphuric acid and into this solution there are introduced, at 20 C., 5g. kolloplexground 8-amino- 5-p-toluidino-7-fl-oxyethylmercapto 1,4dihydroxy-anthraquinone. To this suspension are added 0.1 part iodineand 0.2 part bromine. After the mixture has been heated to 40 C. for 2hours, it is added to a mixture of 300 parts water and 5 parts 40% NaHSOsolution, filtered ofi cold with suction and washed with hot water. Thebromination product contains 1.9% bromine, and when dyed according toExample l(b) gives, on polyester material, green shades of goodlight-fastness and outstanding fastness to thermofixation.

EXAMPLE 24 7.6 parts5,8-diamino-7-phenylmercapto-l,4dihydroxyanthraquinone are dissolved in64 parts 87% sulphuric acid which contain 2.7 parts boric acid, and 0.1part iodine and 0.64 part bromine are added. The reaction mixture isheated to 40 C. within 2 hours and this temperature is maintained for afurther 2 hours. The mixture is added to a mixture of 350 parts waterand 12.5 parts 40% NaHSO solution, heated to 70 C., filtered oif withsuction, washed neutral and dried. The bromination product contains 4.8%bromine and dyes polyester material in clear, greenish-blue shades ofgood fastness to sublimation and light and is distinguished byoutstanding a'ffinity. By increasing the amount of bromine, productswith higher bromine content up to 17.0% are obtained. The more bromineis introduced, the more strongly is the shade shifted to deeper hues.

Bromine Amount content, Ex. Startingmaterial bromine percent Shade25.--. 5,8-diamino-7-m-methyl- 0.32 1.9 Clear,

phenyl-mercapto-L4- greenish dihydroxy-anthrablue. qumone. 26.---5,8-diamino-7o-methyl- 0.96 8.8 D0.

phenyl-mereapt0-1,4- dihydroxy-anthraquinone.

EXAMPLE 27 3.9 parts potassium are dissolved in 85 parts glycolmonoethylether and then 8.5 parts 7-bromo-8-amino-5-anilino-1,4-dihydroxy-anthraquinone are introduced. The reaction mixtureis heated to 125 C. for 12 hours and, after cooling, 50 parts Wateradded dropwise. The crystallized reaction product is filtered olf withsuction and washed with a mixture of 42 parts glycolmonoethyl ether and25 parts water. After washing with water, the residue is boiled out in100 parts acidified water, filtered off with suction and dried. The dyewhich is obtained gives, on polyester material, dyeings in clear,greenish-blue shades of good fastness to sublimation when dyed accordingto Example 1(a).

EXAMPLE 28 8.8 parts7-bromo-8-amino-5-p-toluidino-l,4-dihydroxyanthraquinone, 5.6 partspotassium carbonate, 90 parts chlorobenzene and 6.4 parts thioglycol areheated to 130 C. for hours, filtered ofiE cold with suction and washedwith chlorobenzene and methanol. The residue is boiled up in 200 partsacidified water, filtered off with suction and washed neutral. The dyeobtained is identical with the dye obtained according to Example 2.

EXAMPLE 29 A similar dye to that according to Example 28 is obtainedwith 8.8 parts 7-bromo-8-amino-5-p-toluidino-1,4-dihydroxy-anthraquinone, 6.6 parts sodium acetate, 90 partsglycolmonoethyl ether and 6.4 parts thioglycol are heated to 130 C. for9 hours and the crystalline product which is formed during coolingfiltered olf with suction, washed with glycolmonoether and methanol andworked up otherwise as described in Example 28.

EXAMPLE 30 10.1 parts 7-bromo-5-p-toluene sulphamido-S-amino-1,4-dihydroxy-anthraquinone, 1.7 parts potassium carbonate, 0.1 partcopper oxide, 1 7 parts o-dichlorobenzene and 2.4 parts thiophenol areheated to 110 C. for 2 hours and diluted at 30 C. with parts methanol.After 30 minutes, filtration with suction is effected, followed bywashing with methanol and hot water. After boiling out with dilutehydrochloric acid, the residue is filtered ofi with suction, washedneutral and dried. 9.9 parts =93% of the theory)7-phenylmercapto-5-p-toluenesulphamido-8-amino-1,4-dihydroxy-anthraquinone are obtained. The dye is identicalwith that prepared according to Exam ple 15.

According to method 1(d) there is obtained on polyester a blue dyeing ofvery god fastness to sublimation and light. By hydrolysis in 85%sulphuric acid a dye is obtained which is identical with that fromExample 8.

EXAMPLE 31 4 parts7-bromo-8-amino-5-methylamino-1,4-dihydroxyanthraquinone, 2.3 partssodium carbonate, 40 parts glycolmonoethyl ether and 2.4 partsthiophenol are heated to 120 C. for 1 hour. The crystallized product isfiltered off with suction and washed with glycolmonoethyl ether and hotwater. The substance is boiled out in 100 parts acidified water, washedneutral and dried. Yield: 3.6 g.=83.5% of the theory. Dyed according toExample 1(c), a blue-green dyeing of good fastness is obtai ed.

8 EXAMPLE 32 12.1 parts 7-bromo-8-amino-S-p-toluenesulphamido-1,4-dihydroxy-anthraquinone, 7.0 parts sodium carbonate and 20 parts phenolare heated to 150 C. for 2 hours. 20 parts methanol are added to 60 C.and the crystallized product filtered ofl with suction and washed withmethanol and hot water. The residue is boiled out in 150 parts acidifiedwater, filtered ofl with suction and washed neutral. Yield: 9.3 g.'=75%of the theory. Dyed according to method 1(d), a reddish-blue dyeing ofgood fastness is obtained.

By hydrolysis in sulphuric acid, a dye is formed which is identical withthat described in Example 19.

EXAMPLE 33 5.4 parts 7-phenoxy-5,8-diamino-1,4-dihydroxy-anthraquinonein 54 parts 78% sulphuric acid are brominated at 20 to 25 C. with 05part bromine. The mixture is poured into ice water, filtered oil withsuction and washed neutral. 5.5 parts of a dye (3.3% bromine) areobtained which according to method 1(b) gives reddish-blue, fast dyeingson polyester material.

EXAMPLE 34 9.2 parts7-bromo-8-amino-5-p-chloroanilino-1,4-dihydroxy-anthraquinone, 3.2 partssodium carbonate, parts glycol-monoethylether and 2.3 parts thioglycolare heated to 120 C. for 1 hour. The crystallized reaction product isfiltered off with suction and washed with glycolmonoethyl ether andmethanol as well as water. The residue is boiled out in parts acidifiedwater, filtered off hot with suction, washed neutral and dried. Yield:4.5 parts=50% of the theory. Dyed according to Example 1(d), the dyegives on polyester material bluish-green shades of very good fastness tosublimation and light.

EXAMPLE 35 If, in the previous example, the 7-bromo-8-amino-5-pchloroanilino-1,4-dihydroxy-anthraquinone is replaced by thecorresponding m-chlorine derivative, 7-oxyethylmercapto-8-amino5-m-chloroanilino-1,4 dihydroxy anthraquinone is obtained in 60% yield.

In admixture with the dye prepared according to Example 34, there isobtained according to method 1(c) a bluish-green dyeing of very goodfastness to sublimation and light.

EXAMPLE 36 18.2 parts 7bromo-8-amino-5-o-anisidino-1,4-dihydroxyanthraquinone, 3.2 parts sodiumcarbonate and 20 parts thioglycol are heated to C. for 1 hour, dilutedat 70 C. with 30 parts methanol, filtered ofi with suction and washedwith methanol; this is followed by boiling out in 200 parts acidifiedwater, filtering off with suction, washing neutral and drying. 15.4parts (=85% of the theory) 7 hydroxyethylmercapto 8 amino 5 oanisidino1,4 dihydroxy anthraquinone are obtained. The product is identical withthat prepared according to Example 4.

EXAMPLE 37 A mixture of 50 parts phenol and 4 parts powdered potassiumhydroxide is heated to the boil for half an hour, in order to remove thewater which is formed during the formation of potassium phenolate. Themixture is then cooled to about 120 C.; 15 parts 5-anilino-7-bromo-8-amino-1,4-dihydroxy-anthraquinone and 0.3 part copper powder areintroduced and stirring effected for about 10 hours at C. When startingmaterial can no longer be detected chromatographically, cooling to about70 C. is allowed to take place and dilution with 60 parts methanol iseffected; this is followed by filtration (cold) with suction and washingwith methanol and hot water. The suction filter cake is then boiled outwith dilute hydrochloric acid. There are obtained about 15 parts DyeingAccording to Example Shade Yield, Percent 88.--. -anilino-7-(2-methyl- Po w-wmmo-mdihydroxy-anthraguinone.

39- 5-ani1inq-7-(3'-metbylphenOnfl-S-amino-IA- dihydroxy-anthraquinone.

40.. 5-anilino-7-(4'-methy1- phenoxy)-8-amino-1,+ dihydroxy-anthratnnone.

41.-.- fi-anlltno- -(2'-ethyl-phenoxy)- 8- -L4-dihydroxyanthraquinone.

42.... 5-an1lino-7-(4-tert.butylp o y)-s-amino-1,4-dihydroxy-anthraquinone.

44...- 5-anilino-7-(4-chlorophenoxy)-8-amino-1, 4-dihydroxy-anthraqmnone.

capto-phenoxy)-8-amln0-1,4- dihydroxy-anthraquinone.

40--.. 5-ahilino-7-(3'-metbyl-4'- methylmercapto -phenoxy)-S-amino-lA-dihydroxsranthtaquinone.

Dye

Greenish blue.

1d Do 1d Do.

86 1d Do.

Example 47 5 parts 5-anilino-7-phenoxy-8-amino-14dihydroxy-anthraquinoneare dissolved in 85 par-ts 78% sulphuric acid, and 0.3 part bromine areadded dropwise, with stirring, at 25 C. Stirring is continued for 1hour, followed by emptying into 500 parts water, filtration with suctionand washing neutral. The reaction product contains 2.8% bromine. Onpolyester material there is obtained according to Example 1(b) and 1(c)a full, greenish-blue dyeing of very good fastness to sublimation andlight.

EXAMPLE 48 5 parts 5 anilino 7phenoxy-8-amino-1,4-dihydroxyanthraquinone, 2 parts sodium carbonate and50 parts ethyleneglycol are stirred together for 4 hours at 140 C. Themixture is allowed to cool, diluted with methanol and the homogeneous,crystallized 5-anilino-7-fi-hydroxyethoxy 8amino-l,4-dihydroxy-anthraquinone is filtered off with suction.Polyester fibres are dyed according to Examples 1(b) and 1(0)greenish-blue with very good fastness to sublimation and light.

The dye can also be obtained at 120 C. from S-anilino- 7-bromo 8amino-1,4dihydroxy-anthraquinone, sodium carbonate and ethyleneglycol.

EXAMPLE 49 0.3 part bromide are added dropwise at 25 C., with stirring,to a solution of 5 parts 5-anilino-7-p-hydroxyethoxy8-amino-1,4-dihydroxy=anthraquinone in 85 parts 78% sulphuric acid;stirring is continued for a further hour, followed by working upaccording to Example 47. The reaction product contains 1.8% bromine.Dyed according to Examples 1(b) and 1(0), it dyes polyester materialheavily greenish-blue with very good fastness to sublimation and light.

EXAMPLE 50 5 parts 5 anilino 7phenoxy-8-amino-1,4-dihydroxyanthraquinone, 2 parts sodium carbonate and50 parts glycolmonomethyl ether are stirred together for 24 hours at 120to 125 C. This is followed by cooling, dilution with methanol, filteringolf cold with suction and wash- Dyeing Accord- Yield, lngto Ex. percentExample Shade 51...- 5-anilino-7-n-but0xy-8-amino- 82 1b,1c Greenish1,4-dihydroxyonthrablue.

quinone. 52..-. 5-anilino-7-( -hydmxy-n- 73 1c Do.

hexoxy)-8-amino-1,4- dihydroxy-anthraquinone.

EXAMPLE 53 30 parts5-o-anisidino-7-bromo-8-amino-1,4-dihydroxyanthraquinone and 0.5 partcopper powder are introduced at about C. into a potassium phenolatesolution prepared according to Example 37 from 100 parts phenol and 8parts powdered potassium hydroxide, and the mixture is stirred for 5hours at 170 C. The starting material is then consumed. The melt isstirred into 200 parts methanol and a little water is added; this isfollowed by filtering off cold with suction and washing well withmethanol and hot water, after which the suction filter cake is boiledout with dilute hydrochloric acid. There are obtained in this way about28.7 parts (=93% of the theory) 5-o-anisidino- 7 phenoxy 8 amino 1,4dihydroxy-anthraquinone. The dye, when dyed according to Examples lib)and 1(0), gives on polyester material a bluish-green dyeing of very goodfastness to sublimation and light. 1

EXAMPLE 54 5 parts5-o-anisidino-7-phenoxy-8-amino-1,4-dihydroxyanthraquinone, 2 partssodium carbonate and 50 parts benzyl alcohol are heated, with stirring,to 160 C. for 6 hours and to 180 C. for 2 hours. After the mixture iscold, filtration with suction and washing with methanol and water areeffected. The dye obtained (5-o-anisidino-7-benzyloxy-8-amino-l,4-dihydroxy-anthraquinone, yield about 3.6 parts),when dyed according to Example 1(b) and 1(c), dyes polyester materialblue-green with very good fastness to sublimation and goodlight-fastness.

A similar dye is formed when, instead of benzyl alcohol, ethyleneglycolis used and the reaction is carried out for 1 hour at C. and for half anhour at C.

We claim:

1. Anthraquinone dye of the fomula wherein R and R independently arehydrogen, alkyl containing up to 6 carbon atoms, benzyl, phenethyl,cyclohexyl or phenyl, R and R being optionally substituted with halogen,hydroxy, lower alkyl, lower alkoxy, cyano, amino, nitro or lower alkoxycarbonyl;

X is alkylthio, phenylthio, or phenylthio substituted with hydroxyl,alkoxy, halogen, lower alkyl or alkylthio. 2. The dye of claim 1 whereinR and R are hydrogen or phenyl; and X is alkylthio or phenylthio.

1 l 1 2 3. Anthraquinone dye of the formula References Cited NH: C 011UNITED STATES PATENTS 2,672,464 3/1954 Salvin et a1. 260-380 R1 5FOREIGN PATENTS A 1,180,473 10/1964 Germany 260-380 NH: 0 H

L R N wherein R is hydrogen, halogen or alkyl of 1-4 carbon 0 RAI E A WQ Primary Exammer atoms 10 R. GERSTL, Asslstant Exammer 4. Thedye ofclaim 1 of the formula NH, 0 OH US. Cl. X.R.

1 8-39, 40; 260-396, 379 cmoms 15 NH: O H

